Light-sensitive color photographic material with reduced fog and no decrease in speed during development

ABSTRACT

Fog is reduced and speed is maintained during development of light-sensitive color photographic materials which comprise at least one of certain mercaptotetrazole compounds and at least one of several hydroquinone compounds.

United States Patent Sakamoto et a1. 14 1 Jan. 25, 1972 [s41 LIGHT-SENSITIVE COLOR [561 References Cited PHOTOGRAPHIC MATERIAL WITH UNITED STATES PATENTS REDUCED FOG AND NO DECREASE IN 2 465 149 3/1949 De h l /l 9 rsc et a SPEED DURING DEVELOPMENT 2,728,659 12/1955 Lorin et al. ...96/ 109 *[72] Inventors: Keiiro Sakamoto; Isamu Fushiki; Shinichi 2,981,624 4/1961 Dersch et a1 ..96/109 Nakamura, all of Tokyo, Japan Primary Examiner-Norman G. Torchin [73] Asslgnee' xozshlgoku Photo Industry Assistant Examiner-Alfonso T. Suro Pico To apan Attorney-Waters, Roditi, Schwartz & Nissen [22] Filed: July 9, 1970 [57] ABSTRACT [21] Appl. No; 53,657

Fog is reduced and speed is maintained during development of v light-sensitive color photographic materials which comprise at [30] Foregn Apphcauon Pmmty Data least one of certain mercaptotetrazole compounds and at least July 10, 1969 Japan ..44/541 16 one of Several hydwquinone compounds.

52 us. c1 ..96/109, 96/100, 96/120, 7 n'awings 96/122, 96/125 [51] Int. Cl ..G03c UB4 [58] Field of Search ..96/109, 120, 125, 100, 122

p 3 ,6 3 7 ,3 9-3 1 2 LIGHT-SENSITIVE COLOR PHOTOGRAPHIC (-2 (1 llq N-(1 +4 ll MATERIAL WITH REDUCED FOG AND NO DECREASE I [N SPEED DURING DEVELOPMENT N The present invention relates to a light-sensitive color -5 (ll-3 (i H photographic material free from formation of fog due to color i; l development and further free from degradation in speed.

A color photographic material is composed of emulsion layers larger in number than those in the case of a white-black (1)1 film, so that the thickness of the overall emulsion layer Q becomes great to bring about such a drawback that the resulting image is deteriorated in sharpness. In order to overcome this drawback, there have been made efforts to make the (1H thickness of each layer as thin as possible. If the thickness of (fl-- -NOs 11 each layer is desired to be made thin, the color density should i H necessarily be increased, and thus there are required such means as to increase the contents of coupler and silver halide, Ni with the result that fog is liable to be formed at the time of (1)43 color development. Further, the amount of fog increases when f fi' S n the temperature or the pH of color developer is increased in N N order to develop the photographic material quickly. 01 \\\N/ For the prevention of fog due to color development, there have been used a tetrazaindene compound or a compound (D4 Q having a mercapto group. However, the former is insufficient II in fog-inhibiting effect and hence cannot be put into practical use. Although the latter can inhibit the formation of'fog due to l g p N 7 color development of light-sensitive silver halide, it undesirably brings about severe decrease in speed. tlir- N-C S II We have made extensive studies on processes for preventing Q N color photographic material from decrease in speed to find the CH: fact that when the photographic material is incorporated with H r N r the aforesaid mercapto type compound in combination with a (1)9 hydroquinone-type compound represented'by the general for- H mula set forth below, not only the amount of fog formed due to color development can be greatly decreased but also the decrease in speed at the time of color development can be (1)-10 prevented. C|:H25O-NC S H it is therefore an object of the present invention to provide a light-sensitive color photographic material which has been made less in speed decrease and prevented from formation of 40 fog due to color development by addition of at least one mer- H captotetrazole compound represented by the general formula C N C SH (l):

wherein R R and R are individually a hydrogen atom, an (ll-13 CH N C an alkyl aryl or aralkyl group, provided that R, and R; may be same or different, and at least one hydroquinone compound represented by the general formula (II):

I R5 N (1)45 CHKOH?)7CH=CH(CH2)7CHz1T-fi5H l OH II) N N wherein R is an alkyl group having I to 18 carbon atoms; and N R which is in the 5- or 6-position, is a hydrogen atom or an I alkyl group having 1 to l8 carbon atoms. 7 N N N N Typical examples of the compounds represented by the above-mentioned general formulas are shown below, but com- 1 -1 pounds involved in the scope of the present invention are not 7 02m f f S s N limited only to these. N N N N Examples of the Compound (1): 7O r (1) -l H'N (1)18 a rnr n- N N N N ll II N N Examples of the Compound (II):

(ID-L U" (l llyhnul l hHP I O D-8 OH (ID-9 on (t) CrHn nHaa CruHaa Both the compounds (I) and compounds (ll) of the present invention may be used in admixture of two or more so as to be in conform to the purpose of application of the resulting photographic materials. The compounds (I) and (ll) may be incorporated into one layer or may separately be incorporated into adjacent layers. These compounds may be incorporated not only into emulsion layers but also into auxiliary layers such as sub layer, inter layer, protective layer and the like. F urther, the compounds may be added to a silver halide emulsion at any stage during the preparation thereof, but it is more effective to add the compounds at a stage during the second ripening or a stage prior to coating the emulsion to a support.

The amounts of the compounds to be added are not particularly limited, and the optimum amounts thereof vary depending on the kinds of the compounds. Generally, however, the amounts of the compounds (I) and (ll) are preferably 10 to 10" moles and 10 to 10* moles, respectively, per mole of silver halide. Among the compounds (I) and (ll), those which are lipophilic are added in the form of solutions in a high boiling organic solvent such as dibutyl phthalate or the like or in a low boiling organic solvent such as chlorofomi, acetone, dimethylformamide or the like, while those which are watersoluble are added in the form of solutions in a water-miscible organic solvent or an aqueous alkali solution.

The photographic emulsion used in the present invention include AgCl, AgBr, AgClBr, AgBrl and the like. The emulsion may be optically sensitization treatment with a cyanine or merocyanine dye or to chemically sensitized treatment with a sulfur-containing compound (sodium thiosulfate), noble metal salt (gold chloride), polyalkylene oxide derivative, reducing compound or the like. Further, the emulsion may have been incorporated with such a hardener as formalin and such a coating aid as a synthetic or natural surface active agent, e.g., saponin. The color couplers which are used in the present invention are those which develop colors through the reaction with a p-phenylenediamine color developer. Generally, there may be used a yellow coupler having a benzoylacetanilide group, a magenta coupler having a pyrazolone or indazolone group, and a cyan coupler having a phenol or naphthol group. These couplers may contain in the active methyleneor methine-portion a substituent capable of releasing by color development reaction, e.g., a halogen or an arylazo, aryloxy or the like group. Further, the couplers may contain in the molecule either one or both of a ballasting group, e.g. a long chain alkyl group or an alkylphenoxy group,

and a water-solubilizing group, e.g., a sulfonic group or a carboxyl group. Among these couplers, those which are lipophilic may be brought into the form of solutions in a high boiling organic solvent, e.g., dibutyl phthalate, or in a low boiling organic solvent, e.g., chloroform, acetone or dimethylformamide, while those which are water-soluble may be brought into the form of solutions in an alkali or the like, and the solutions may be added directly to a silver halide emulsion or added to a color developer.

The light-sensitive layer of the photographic material according to the present invention is composed of, from the top layer, a protective layer, a yellow layer, a yellow filter layer, a magenta layer, an inter layer, a cyan layer, an antihalation layer and a support in this order. Alternatively, the light-sensitive layer may be composed of a magenta layer, a cyan layer and a yellow layer in this order. in each case, the photographic material can be used effectively.

The support employed in the present invention includes natural and synthetic polymer films such as cellulose acetate or polyester film.

Typical examples of the color developing agent used for the development of the present light-sensitive photographic materials are sulfates, hydrochlorides and sulfites of N,N- diethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-2-methyl-p-phenylenediamine, N-ethyLB-N-methanesulfonamidoethyl-3- methyl-4-aminoaniline, and the like.

in order to illustrate wide applications of the present invention, several examples are set forth below, but it is needless to say that the present invention is not limited to these examples but various modifications are possible within the scope of the invention.

EXAMPLE 1 A high-speed silver bromoiodide photographic emulsion (containing 5.0 mole of Ag! and 180 g./mole AgX of gelatine) was incorporated with 2.5Xl moles/mole AgX of a sensitizing dye having the structure set forth below to prepare a red light-sensitive emulsion.

To the thus prepared emulsion was added the compound (l)4 in such an amount as shown in table 1. Thereafter, 2 kinds of color couplers of the structures shown below and the compound (ll)-9 were added insuch amounts as shown in table 1.

Coupler 1:

Coupler 2:

l N H N l Subsequently, the resulting mixture was subjected to a highspeed mixer to form a dispersion of the composition shown below in which the amounts of the constituents were per mole of AgX.

Composition of dispersion Coupler l 10 g. Coupler 2 4 Compound (Il)-9 Variable amount Tricresyl phosphate 20 g. Ethyl acetate l5 g. 2% Gelatine 400 ml. 5% Alkanol B (tradename of Du Four) 15 ml.

Subsequently, the dispersion was coated on a cellulose triacetate film to a dry thickness of 45p, and then dried to obtain a photographic film. This film was subjected to definite exposure through an optical wedge and then to the following color development treatment:

I. Color development 20 C., 12 min.

Composition of developer Benzyl alcohol 3.8 ml. Sodium sulfite (anhydrous) 2.0 g. N-ethyl-N-fimethanesulfonamidoethyl-3-mcthyl-4-aminoanilinc sulfate 5.0 g. Sodium carbonate (monohydrate) 50.0 g. Potassium bromide 1.0 g. Water to make L000 ml. 7

The pH was adjusted to 10.8 by addition of caustic soda.

. First fix 20 C., 5 min.

Composition of fixing solution Sodium thiosulfate g. Water to make 1.000 ml.

3. Wash 5 min.

4. Bleach 20 C., 6 min.

Composition of leaching solution Potassium ferricyanide 100.0 g. Potassium bromide 50.0 g. Water to make L000 ml.

5. Wash 5 min.

6. Second fix The composition of fixing solution was same as in the first fixing.

7. Wash l0 min.

8. Dry

The film after the color development treatment was measured in density by use of a red filter to obtain the results shown in table I.

From the results shown in table 1, it is understood that when the compound (U4 is used in combination with the compound (ll)9, there are obtained color films which are less in fog and higher in speed than in the case where the compound (0-4 is used alone.

EXAMPLE 2 The same red light-sensitive emulsion as in example l was incorporated with each of the combinations of the compounds (I) and (II) as set forth in table 2. The compound (I) was used in an amount of 8.2Xl0' moles/mole AgX, and the compound (ll) in an amount of 6Xl0' mole/mole AgX. The test methods employed were the same as in example 1. The results were as shown in table 2.

emulsion as in example 1 was incorporated with. 3.l l moles/mole AgX of a sensitizing dye having the structure shown below to obtain a green light-sensitive emulsion.

( CsHu The dispersion had the composition shown below in which the amounts of the constituents were per mole of AgX.

Composition of dispersion Coupler 56 g. Tricresyl phosphate g. Ethyl acetate g. 2% gelatin: 500 ml. 5% Alkanol B 21 cc.

Subsequently, the dispersion was coated on a cellulose triacetate film to a dry thickness of 5p. and then dried to form an emulsion layer on the film. Onto this emulsion layer, each of dispersions of protective layers 1 and 2 of the compositions shown below was coated to a dry thickness of lu, and then dried.

TABLE 2 Compositions of protective layers e ativs Protective Protective p n (I) Compound (II) speed Fog 2 H 5 Compound (ll)-7 0 5.0 g. Compound (0-2 "lgggggggg EHLL Dibutyl phthalate 2.0 g. 2.0 g. Compound (II)9 131 0. D9 Ethyl acetate 5.0 g. 5.0 g. 100 1 2% Gelatine 800 ml. 800 Ill. Compound (1)-7 38:32:33 h g3"- Ei 3-53 5% Alkanol a 7.5 ml. 7.5 ml.

Compound (II)9 138 o. 07 is a; w ompoun compmind (I) 13 Compound (m4... 119 0.10 The film after drying was sub ected to the same color f f f 2 8:23 development treatment as in example 1 and measured in den- 605501113561 108 0.12 sit b means of a reen filter to obtain the results set forth in Cmpmmd (1) 18 Compounding-4." 118 0.11 g g 8 Compound (ID-9. 119 0. 11 1 5 Wwfim TABLE 3 From the results shown in table 2, it is understood that every combination gives a light-sensitive photographic material higher in speed and less in fog than in the case where the com- Relative pound (l) is used alone. 20 speed mg 3 Protective layer 1 (control) 100 0."

Protective layer 2 [containing The same high speed silver bromoiodide photographic the pound (In- I26 0.10

This example shows the case where the compound (I) was added to the emulsion layer and the compound (ll) was added to the protective layer. However, the same effects as above can be obtained also in the case where, conversely, the compound (II) is added to the emulsion layer and the compound (I) is added to the protective layer.

EXAMPLE 4 (IIOOH COOH Thereafter, each of dispersions l and 2 of the compositions shown below was mixed with the above-mentioned emulsion, and the resulting mixture was coated on a film base to dry thickness of 4.044. and then dried. in the dispersions, the amounts of the constituents were per mole of AgX.

Compositions of dispersions Dispersion l Dispersion 2 Compound (ll)-8 0 4 g. Ethyl acetate 8 g. 8 g. 2% Gelatine 600 ml. 600 ml. 5% Alkanol B l8 ml I8 ml.

The film after drying was subjected to definite exposure through an optical wedge and then to development at 20 C. for 10 minutes with the color developer shown below to obtain the results set forth in table 4. The bleaching and fixing treatments were effected in the same manner as in example 1.

Color developer Anhydrous sodium sulfite 2.0 g. 4-amino-N,N'-dielhylaniline hydrochloride 5.0 g. Sodium carbonate (monohydrate) 50.0 g. Potassium bromide 1.0 5. Water to malte L000 ml.

9 TABLE 4 Relative speed Fog Dispersion I (control) Dispersion 2 [containing the compound (ll)-8] Thus, in all the cases where the present invention is practiced in the above manner, the amount of fog formed is less than in the cases where the combinations of the said two compounds were not used, and obvious sensitizing effects are observed.

What we claim is:

l. A light-sensitive gelatinous silver halide color photographic material characterized by containing in at least one of the layers constituting the photographic material at least one mercaptotetrazole compound of the general formula,

wherein R,, R and R are individually a hydrogen atom, an alkyl, aryl or aralkyl group, provided that R and R may be same or different, and at least one hydroquinone compound of the general fonnula,

wherein R is an alkyl group having 1 to 18 carbon atoms, and R which is in the 5- or 6-position, is a hydrogen atom or an alkyl group having I to 18 carbon atoms.

2. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercaptotetrazole compound and said hydroquinone compound jointly exist in a same layer selected from theemulsion layer,

inter layer, sub layer, filter layer and protective layer of the photographic material.

3. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercapgrzzphic material. I

. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercaptotetrazole compound is and said hydroquinone compound is (t) CiH17- --CsH11(t) 7. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercaptotetrazole compound is and said hydroquinone compound is CsH11( 

2. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercaptotetrazole compound and said hydroquinone compound jointly exist in a same layer selected from the emulsion layer, inter layer, sub layer, filter layer and protective layer of the photographic material.
 3. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercaptotetrazole compound and said hydroquinone compound separately exist in the adjacent layers selected from the emulsion layer, inter layer, sub layer, filter layer and protective layer of the photographic material.
 4. A light-sensitive gelatinous silver halide photographic material as claimed in claim 1, wherein either one or both of said mercaptotetrazole compound and said hydroquinone compound are used in combination with a chemical sensitizer or/and an optical sensitizer.
 5. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein a color coupler is also incorporated in the emulsion layer of said photographic material.
 6. A light-sensitive gelatinous silver halide color photOgraphic material as claimed in claim 1, wherein said mercaptotetrazole compound is
 7. A light-sensitive gelatinous silver halide color photographic material as claimed in claim 1, wherein said mercaptotetrazole compound is 